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CN-122011732-A - Halogen-free epoxy resin composition, aerogel packaging film, preparation method and application

CN122011732ACN 122011732 ACN122011732 ACN 122011732ACN-122011732-A

Abstract

The invention relates to a halogen-free epoxy resin composition, an aerogel packaging film and a preparation method and application thereof, wherein the halogen-free epoxy resin composition comprises, by weight, 10-25 parts of halogen-free bisphenol A type epoxy resin, 10-30 parts of halogen-free polyurethane modified epoxy resin, 10-20 parts of halogen-free acrylic modified epoxy resin, 10-35 parts of toughening agent, 20-35 parts of halogen-free flame retardant, 1-10 parts of curing agent, 0.01-1 part of curing accelerator and 0.01-5 parts of stabilizer. The halogen-free epoxy resin composition can be used for preparing aerogel packaging films, can not adhere to an object to be adhered at room temperature, can activate reaction at a lower temperature, has higher peel strength and shearing strength, is excellent in ageing resistance, can prevent flame from passing the requirement of UL 94V-0 level, and can be stored at room temperature for a long time without losing efficacy and increasing logistics and storage cost.

Inventors

  • ZHU ZHONGLU
  • XU MINGLIAN
  • LI JIANXIONG

Assignees

  • 皇冠新材料科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260304

Claims (10)

  1. 1. The halogen-free epoxy resin composition is characterized by comprising the following components in parts by weight: 10-25 parts of halogen-free bisphenol A epoxy resin; 10-30 parts of halogen-free polyurethane modified epoxy resin; 10-20 parts of halogen-free acrylic acid modified epoxy resin; 10-35 parts of a toughening agent; 20-35 parts of halogen-free flame retardant; 1-10 parts of a curing agent; 0.01-1 part of a curing accelerator; 0.01-5 parts of stabilizer.
  2. 2. A halogen-free epoxy resin composition according to claim 1, characterized in that: The halogen-free polyurethane modified epoxy resin is halogen-free polyurethane modified epoxy resin synthesized by synthesizing polyurethane prepolymer from polyhydroxy compound and polyisocyanate and then grafting the polyurethane prepolymer with first epoxy resin, or halogen-free polyurethane modified epoxy resin synthesized by synchronously polymerizing polyhydroxy compound, polyisocyanate and first epoxy resin; the halogen-free acrylic acid modified epoxy resin is prepared by grafting (methyl) acrylic acid on methylene or methine of a second epoxy resin; The toughening agent is at least one of nitrile rubber, styrene-butadiene rubber, ethylene propylene rubber, polyolefin resin, polyamide imide resin and polyurethane toughening agent; the halogen-free flame retardant is at least one of aluminum hydroxide, magnesium hydroxide, organic phosphate and phosphinate; The curing agent is at least one of a linear phenolic resin curing agent, a linear bisphenol A type phenolic resin curing agent, a linear o-cresol formaldehyde resin curing agent, 4' -diamine diphenyl methane, m-phenylenediamine and m-xylylenediamine; the curing accelerator is at least one of microcapsule curing agent, boron trifluoride, imidazole or derivatives thereof, wherein the imidazole or derivatives thereof are at least one of compounds shown in the following structural formula: 、 、 、 、 、 ; The stabilizer is boric acid ester or cyclic boric acid ester compound.
  3. 3. A halogen-free epoxy resin composition according to claim 2, characterized in that: the halogen-free polyurethane modified epoxy resin is at least one of HyPox UA and HyPox UA; The halogen-free acrylic acid modified epoxy resin is at least one of A102 and B-151 DT; The nitrile rubber is CTBN 1300 multiplied by 8, the styrene-butadiene rubber is Buna VSL 5025-2 HM, the butadiene rubber is BR-9000, the ethylene-propylene rubber is EPDM6950, the polyolefin resin is AFFINITYTM GA1950, the polyamide imide resin is Torron 4203L, and the polyurethane toughening agent is Desmocap11A; The flame retardant is a mixture obtained by mixing at least one of aluminum hydroxide and magnesium hydroxide with at least one of organic phosphate and phosphinate according to a mass ratio of 1 (0.8-1.2); the aluminum hydroxide is MARTINAL-906, the magnesium hydroxide is MAGNIFIN H-5 IV, the organic phosphate is PX-200, and the phosphinate is OP930; The linear bisphenol A type phenolic resin curing agent is at least one of TD-2131, KAYAHARD GPH-65, KAYAHARD GPH-103 and KAYAHARD KTG-105, the linear bisphenol A type phenolic resin curing agent is at least one of VH-4150 and KH-6021, the linear o-cresol formaldehyde resin curing agent is at least one of KA-1160 and KA-1165, the 4,4' -diaminodiphenylmethane is ANCAMINE, DL-50, the m-phenylenediamine is MPD, and the m-xylylenediamine is MXDA; The microcapsule curing agent is at least one of HX-3722 and HX-3921HP, the boron trifluoride is OMICURE BC-120, and the imidazole or the derivative thereof is at least one of SIZ, 2MZ-H and 1B2 MZ; the stabilizer is at least one of QXA, L07N, STA-1000.
  4. 4. A halogen-free epoxy resin composition according to any one of claims 1 to 3, characterized in that: The halogen-free epoxy resin composition further comprises an organic solvent; The organic solvent is at least one of toluene, acetone, butanone, cyclohexanone, xylene, propylene glycol methyl ether acetate, N '-dimethylformamide, N' -dimethylacetamide and dimethyl sulfoxide; the halogen-free bisphenol A epoxy resin, the halogen-free polyurethane modified epoxy resin, the halogen-free acrylic acid modified epoxy resin, the toughening agent, the halogen-free flame retardant, the curing agent, the curing accelerator and the stabilizer are dispersed in the organic solvent to form suspension slurry, and the rotational viscosity of the suspension slurry is 500-2000 cps.
  5. 5. The halogen-free epoxy resin composition according to any one of claims 1 to 3, wherein the halogen-free bisphenol A type epoxy resin composition comprises 16-18 parts of halogen-free bisphenol A type epoxy resin, 13-15 parts of halogen-free polyurethane modified epoxy resin, 12-14 parts of halogen-free acrylic modified epoxy resin, 20-21 parts of toughening agent, 28-29 parts of halogen-free flame retardant, 4.7-5.2 parts of curing agent, 0.5-0.6 part of curing accelerator and 0.8-2.2 parts of stabilizer.
  6. 6. An aerogel packaging film, characterized in that: the aerogel packaging film comprises a halogen-free epoxy resin composition layer; the halogen-free epoxy resin composition layer is formed of the halogen-free epoxy resin composition according to any one of claims 1 to 5.
  7. 7. The aerogel packaging film of claim 6, wherein: The aerogel packaging film also comprises a PET film and a PET protection film which are respectively arranged at two sides of the halogen-free epoxy resin composition layer; The PET film is transparent, black or white, and the thickness of the PET film is 3-100 mu m; the halogen-free epoxy resin composition layer is an opaque adhesive layer, and the adhesive coating thickness is 3-100 mu m; The PET protective film is transparent, black or white, and the thickness of the PET protective film is 3-100 mu m; The halogen-free epoxy resin composition layer is formed by drying the halogen-free epoxy resin composition.
  8. 8. The method for preparing an aerogel packaging film according to claim 6 or 7, comprising the steps of: The preparation method comprises the steps of dissolving all components in a halogen-free epoxy resin composition in an organic solvent, mixing to form suspension slurry, coating the suspension slurry on a PET film by using coating equipment, heating the PET film coated with the suspension slurry for 2-6 minutes through an oven at 70-160 ℃ to form a halogen-free epoxy resin composition layer containing a solvent-free solid adhesive film state, then pasting a PET protective film at 50-90 ℃ and 0.05-2.0 MPa, and winding to obtain the aerogel packaging film.
  9. 9. The method of manufacturing according to claim 8, wherein: the suspension slurry is prepared by uniformly mixing all components together through at least one of grinding equipment and high-speed stirring and dispersing equipment; the rotational viscosity of the suspension slurry is 500-2000 cps.
  10. 10. The utility model provides a battery, includes the aerogel of locating between the adjacent battery module, its characterized in that: The aerogel is wrapped by an aerogel packaging film, wherein the aerogel packaging film is the aerogel packaging film according to claim 6 or 7 or the aerogel packaging film prepared by the preparation method according to claim 8 or 9.

Description

Halogen-free epoxy resin composition, aerogel packaging film, preparation method and application Technical Field The invention relates to the technical field of packaging films, in particular to a halogen-free epoxy resin composition, an aerogel packaging film, a preparation method and application. Background Aerogel is a highly dispersed solid material in which the pores are filled with a gaseous dispersion medium, and which is a nanoporous network structure composed of colloidal particles or polymer molecules mutually coalesced by a sol-gel method. The aerogel is light, the heat conductivity coefficient is generally 0.015-0.024W/(m.K), the heat insulation effect is good, and meanwhile, the flame retardance is excellent, and the UL 94V 0 grade can be achieved. In the field of new energy batteries of automobiles, the aerogel composite material is widely applied between the battery cells/modules, plays a role in heat insulation, can also prevent mutual extrusion and friction between adjacent battery modules, and solves the problem of thermal runaway of a battery system to a certain extent. However, the aerogel is easy to crack, fall off powder and fall off, and the aerogel needs to be wrapped by a packaging film when in use, so that the influence of the powder falling on a battery is avoided, and the safety of the aerogel in the assembly process and the service life of the aerogel in a battery pack are ensured. Currently, the common aerogel packaging film is prepared by coating an adhesive on a substrate. The base material generally adopts PET film and polyimide film, and the adhesive system used by the adhesive is various. The acrylic adhesive has long storage time at normal temperature, can be attached to an object to be attached at room temperature, but has low peel strength, generally does not exceed 0.68N/mm, has poor ageing resistance, can only ensure that the phenomena of bulging and layering do not occur at 65 ℃/90% RH/168h, and has the problem of overlarge initial adhesion, influences the positioning during processing, and is difficult to tear for repair after misplacement. The initial adhesion of the polyurethane adhesive system is very low, but the peel strength and the shear strength are low, not more than 0.8N/mm and 1.6MPa, and the ageing resistance is not mentioned. The epoxy resin adhesive has the advantages of good technological performance, high bonding strength, small shrinkage, excellent dielectric property, good electrical insulation property, high peeling and shearing strength after complete curing, strong aging resistance and difficult adhesive opening even if immersed in an organic solvent, but the conventional epoxy resin adhesive has shorter storage life at normal temperature and usually needs to be stored at low temperature (0-10 ℃), so that the use of the epoxy resin adhesive is limited and the logistics and storage cost is increased. Disclosure of Invention Aiming at the defects of the prior art, the first object of the invention is to provide a halogen-free epoxy resin composition which can be used for preparing aerogel packaging films, has no viscosity at room temperature and can not adhere to an object to be adhered, can activate reaction at a lower temperature, has higher peel strength and shear strength, has excellent ageing resistance, and can prevent flame from passing the requirement of UL 94V-0 grade, and can not fail after being stored at room temperature for a long time, so that logistics and storage cost can not be increased. A second object of the present invention is to provide an aerogel packaging film prepared from the halogen-free epoxy resin composition. A third object of the present invention is to provide a method for preparing the aerogel packaging film. A fourth object of the present invention is to provide the use of the aerogel packaging film. The invention provides a halogen-free epoxy resin composition, which comprises, by weight, 10-25 parts of halogen-free bisphenol A type epoxy resin, 10-30 parts of halogen-free polyurethane modified epoxy resin, 10-20 parts of halogen-free acrylic modified epoxy resin, 10-35 parts of toughening agent, 20-35 parts of halogen-free flame retardant, 1-10 parts of curing agent, 0.01-1 part of curing accelerator and 0.01-5 parts of stabilizer. In some embodiments of the invention, the halogen-free polyurethane modified epoxy resin is a halogen-free polyurethane modified epoxy resin synthesized by synthesizing a polyurethane prepolymer from a polyhydroxy compound and polyisocyanate and then grafting the polyurethane prepolymer with the first epoxy resin, or is a halogen-free polyurethane modified epoxy resin synthesized by synchronously polymerizing the polyhydroxy compound, the polyisocyanate and the first epoxy resin. In some embodiments of the present invention, the halogen-free acrylic modified epoxy resin is prepared by grafting (meth) acrylic acid onto the methylene or methine group of the second epoxy resin. In some